CN1711285A

CN1711285A - Optical members and compositions for producing them

Info

Publication number: CN1711285A
Application number: CN 200380103409
Authority: CN
Inventors: 保田贵康; 佐佐木广树; 根守良一; 冈本裕一
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2002-11-15
Filing date: 2003-11-14
Publication date: 2005-12-21
Anticipated expiration: 2023-11-14
Also published as: CN100368826C

Abstract

It is disclosed a polymerizable composition for producing an optical member for 850 nm wavelength comprising: a polymerizable monomer composition and a compound, having a different refractive index from that of the polymerizable monomer composition, whose structure has a benzene ring substituted by a substituent having a Hammett value of not greater than 0.04 or by plural substituents having an average value of Hammett values thereof of not greater than 0.04. It is also disclosed a polymerizable composition for producing an optical member comprising a polymerizable monomer composition comprising at least one selected from the group consisting of C7-20 alicyclic (meth)acrylates and a compound, having a different refractive index from that of the polymerizable monomer composition and having a solubility parameter of not greater than 10.9, whose structure has a benzene ring substituted by the substituent or the substituents defined above.

Description

The composition of optical component and the described member of production

Technical field

The present invention relates to plastic optics component technology field, particularly relate to the plastic optics component technology field that preferably can be used for plastic optical fiber, photoconduction or optical lens, and relate to the polymerisable compound of producing described plastic optics member.

Background technology

In recent years, the plastic optics member owing to its than the quartz with same structure-Ji optical component can be with lower cost, produce more simply and the advantage of processing treatment has obtained widespread use, comprise as optical fiber, photoconduction and optical lens.Because the whole zone of its cell fiber is made by plastic material and therefore have big slightly transmission loss, therefore the quality of plastic optical fiber is worse than quartz-Ji fiber slightly, but what it was better than quartz-Ji fiber is: have excellent flexibility, in light weight, workability, better application and lower cost in producing big core diameter.Therefore, for plastic optical fiber as the optical fiber that can in short relatively distance, work, to ignore its bigger transmission loss, the transmission medium that described optical fiber is used for optical communication has carried out studying (referring to KYORITSU SHUPPAN CO., the 1-8 page or leaf of " Plastic Optical Fiber " that LTD. published in 1997 and edited by POF Consortium).

Plastic optical fiber has usually: formed and comprise the central cores (being called " core district " in specification sheets) of polymeric matrix and formed the shell (being called " clad region " in specification sheets) that specific refractory power is different from core district (being usually less than the core district) by organic compound by organic compound.Particularly, have the plastic optical fiber of gradation refractive index to its external direction along the center, i.e. GI plastic optical fiber, as the optical fiber that can guarantee the high-transmission ability, it has attracted a lot of attentions recently.Proposed to prepare a kind of method of described plastic optical fiber, this method comprises: form fiber base member (being called " preformed articles " in specification sheets) according to interface gel polymerization, then to preformed articles stretch (referring to KYORITSU SHUPPAN CO., the 66-72 page or leaf of " Plastic Optical Fiber " that LTD. published in 1997 and edited by POFConsortium; WO93/08388 or the like).

Require optical launcher almost not have transmission loss and have high transmission capacity.Particularly, when plastic optical fiber used with the light source of launching near infrared light such as 850nm light, the absorption of interatomic bond stretching vibration overtone was the factor that transmission loss increases.Knew already that c h bond was the body material that constitutes plastic optical fiber, and the absorption of c h bond stretching vibration overtone will make transmission loss worsen; Therefore usually with heavier atom such as deuterium or fluorine atom displacement H atom (referring to KYORITSU SHUPPAN CO., the 41-66 page or leaf of " plastic optical fiber " that LTD. published in 1997 and edited by POFConsortium).For the distribution of regulating specific refractory power and guarantee that between core and cladding regions specific refractory power has enough differences and is added into known compound in the body material, be called " specific refractory power toughener " or " doping agent ", it can be not polymerisable or polymerisable compound, nearly all this compound all has at least one phenyl ring, and knew already that the absorption of C-H stretching vibration the 4th overtone will increase transmission loss in the phenyl ring.Therefore, refractive index toughener and body material have carried out deuterate (referring to the 20-22 page or leaf of WO93/08488).Deuteration can make transmission loss obviously reduce, yet other problem can occur, and is too expensive usually as the deuterated material, and available compound also only is confined to a spot of several.

It is also known that in addition the consistency between body material and the doping agent has tangible influence to transmission loss.It is also known that in addition because the absorption of OH stretching vibration overtone, the hydrophobicity of body material that comprises doping agent is influential to transmission loss near the 850nm wavelength region.

Summary of the invention

One object of the present invention is, a kind of polymerisable compound that can produce the optical component that is used for the 850nm wavelength at low cost is provided.

Another object of the present invention is to, provide a kind of optical component that has the low transmission loss at the 850nm wavelength with low cost.

Another object of the present invention is to, provide a kind of and can produce the polymerisable composition that has low transmission loss and good water-fast-stable on heating optical component at the 850nm wavelength.

Another object of the present invention is to, provide a kind of with low cost and have low transmission loss and good water-fast-stable on heating optical component at the 850nm wavelength.

The present inventor has carried out various researchs, found that, has incidence relation between the substituent Hammett value on the absorption peak of C-H stretching vibration the 4th overtone and the phenyl ring in the phenyl ring; And when phenyl ring is replaced to electron substituent group, described absorption peak will move to the long wave direction.Find again further research based on these, aspect solubility parameter, the hydrophobic composition of for example doping agent and body material studied that the result has finished the present invention.

On the one hand, the invention provides the polymerisable compound that a kind of production is used for the optical component of 850nm wavelength, described composition comprises:

Polymerizable monomer component,

Polymerization starter and

Specific refractory power is different from the compound of described polymerizable monomer component, has the phenyl ring of a plurality of substituting groups replacements that are not more than by the Hammett value that substituting group of 0.04 replaces or are not more than 0.04 by Hammett value mean value in its structure.

As embodiment of the present invention, provide following polymerisable compound: (1) wherein, described polymerizable monomer component comprises at least a monomer that is selected from the ester of acrylic acid ester and its derivative that accounts for major portion; (2) wherein, polymerizable monomer component comprises the monomer of the ester of the acrylic acid ester of at least a being selected from (methyl) that accounts for major portion and its derivative; (3) wherein, polymerizable monomer component comprises at least a material that is selected from the compound with C-F key; And (4) polymerizable monomer component comprises at least a material that is selected from the compound of (deuterium) key that has C-D.

On the other hand, the invention provides the optical component of producing by the polymerization of described composition, so that form zone with gradation refractive index.

On the other hand, the invention provides the optical component that is used for the 850nm wavelength, described member comprises:

The polymer composition that comprises at least a polymkeric substance, described polymkeric substance be selected from (methyl) acrylate based polyalcohol and

Have the compound of different refractivity with the polymerizable monomer component of described polymer composition, wherein, described compound be not shorter than the 875nm place have owing to phenyl ring in the absorption peak of c h bond stretching vibration the 4th overtone.

As embodiment of the present invention, provide wherein said compound to be selected from following structural formula

(1) optical component:

Structural formula (1)

Wherein, R ¹-R ¹⁰Represent hydrogen separately, alkyl, alkenyl, alkoxyl group, alkenyloxy or dialkyl amido, precondition is wherein to represent alkyl, alkenyl, alkoxyl group, alkenyloxy or dialkyl amido at least four; Provide and comprise optical component with gradation refractive index zone; And comprise along the center to the optical component with gradation refractive index zone of external direction.

On the other hand, the invention provides a kind of polymerisable compound that is used to produce optical component, described composition comprises:

Comprise at least a compound polymerizable monomer component that is selected from following structural formula (2):

Structural formula (2)

Wherein, X ¹Be hydrogen (H) or deuterium (D), wherein two X ¹Can be identical or different; Y ¹Expression H, D, CH ₃Or CD ₃R ¹Expression C _7-20Alicyclic hydrocarbon radical;

Polymerization starter and

Specific refractory power is different from described polymerizable monomer component and solubility parameter is not more than 10.9 compound, has the phenyl ring of a plurality of substituting groups replacements that are not more than by the Hammett value that substituting group of 0.04 replaces or are not more than 0.04 by Hammett value mean value in its structure.

As embodiment of the present invention, provide following polymerisable composition: (1) wherein, polymerizable monomer component comprises methacrylic acid alicyclic ring family's methyl esters and the methyl methacrylate that accounts for major portion; (2) wherein, polymerizable monomer component comprises the compound of at least a C-D of having key.

As embodiment of the present invention, provide to comprise optical component by described composition polymerization core district that makes and the cladding regions that covers described core district with gradation refractive index; Gradation refractive index in the core district is to the optical component of the direction of outside along the center; The optical component that cladding regions is formed by polymerizable monomer component substantially, described polymerizable monomer component comprise the composition identical with the core district or most of identical composition; And as the optical component of optical fiber, photoconduction or optical lens.

On the other hand, the invention provides a kind of method that is used to produce optical component, described method comprises makes above-mentioned polymerisable compound step of polymerization.

As embodiment of the present invention, the method that comprises described polymerization procedure is provided, wherein polymerization temperature is 50 ℃ or higher.

Embodiment

Embodiment of the present invention will be described in detail belows.

The example that it is pointed out that the optical component that composition polymerization according to the present invention is produced comprises: light guide such as optical fiber or photoconductive tube; Be used for frequency still camera, camcorder, visual telescope, glasses, the lens of plastic contact lens or solar collector; Mirror such as concavees lens or polygon mirror, and prism pentaprism for example.Wherein desirablely be, optical component is applied to light guide, lens or mirror, what more wish is to be applied to optical fiber, photoconduction or lens.

1. polymerisable compound

At first, describe the embodiment of polymerisable compound of the present invention in detail.

First embodiment of 1-1 polymerisable compound

First embodiment of polymerisable compound of the present invention mainly comprises: polymerizable monomer component, the polymerization starter of energy initiated polymerization, and have the compound of different refractivity with monomer component, be sometimes referred to as " doping agent " or " specific refractory power toughener " hereinafter.According to this first embodiment, by utilizing a kind of like this compound can reduce as doping agent because the transmission loss that doping agent brings, this compound has at least one by the phenyl ring of a substituting group replacement or the replacement of a plurality of substituting group, a wherein said substituent Hammett value is in a specified range, and the mean value of described its Hammett value of a plurality of substituting groups is in described specified range.The composition of first embodiment can be used for producing optical component, particularly has the optical component that refractive index value distributes.

Use description to the various materials of first embodiment below.

The 1-1-1 polymerizable monomer component

According to first embodiment, wish that polymerizable monomer component comprises at least a material that is selected from the ester of acrylic acid ester and its derivative that accounts for major portion.The concrete example of the ester of vinylformic acid and derivative thereof comprises acrylate and methacrylic ester, hereinafter all is called " (methyl) acrylate ".Term " comprises the monomer that accounts for major portion " and not only is meant the embodiment of being made up of this monomer, but also refers to also comprise at least a embodiment that is different from described monomeric polymerisable monomer, only otherwise can reduce optical characteristics.Polymerizable monomer component can comprise the monomer and at least a polymerisable monomer such as the vinylbenzene or the maleimide that is selected from except that (methyl) acrylate of at least a being selected from (methyl) acrylate, so that form any multipolymer.When using wherein, can produce optical component, so deuterated (methyl) acrylate is preferred with low transmission loss to small part hydrogen during by the deuterate of deuterium exchange (methyl) acrylate.Utilize fluorizated (methyl) acrylate easily between the multipolymer of the optical fiber that is obtained and non--fluorinated monomer, to form the specific refractory power that differs widely, therefore, can easily produce the fractionated refractive index structures.Therefore, fluorizated (methyl) acrylate is preferred.

Listed the example of useful (methyl) acrylate in the first embodiment, yet described example is not limited to these.

(a) non--fluorizated (methyl) acrylate, as methyl methacrylate, Jia Jibingxisuanyizhi, the methacrylic acid isopropyl esters, methacrylic tert-butyl acrylate, methacrylic acid benzylester, the methacrylic acid phenylester, cyclohexyl methacrylate, methacrylic acid benzhydryl ester, methacrylic acid three ring [5.2.1.0 ^2,6] last of the ten Heavenly stems ester, methacrylic acid adamantane esters, IBOMA, methyl acrylate, ethyl propenoate, tert-butyl acrylate, or phenyl acrylate;

(b) fluorizated (methyl) acrylate, as methacrylic acid 2,2,2-trifluoroethyl ester, methacrylic acid 2,2,3,3-tetrafluoro propyl diester, methacrylic acid 2,2,3,3,3-five fluoropropyl esters, methacrylic acid 1-trifluoromethyl-2,2,2-trifluoroethyl ester, methacrylic acid 2,2,3,3,4,4,5,5-octafluoro amyl group ester or methacrylic acid 2,2,3,3,4,4-hexafluoro butyl ester.

Also can use the polymerisable monomer except that (methyl) acrylate in addition.Listed the example of polymerisable monomer useful except that (methyl) acrylate in the first embodiment, yet described example is not limited to these.

(c) compound of styryl, as vinylbenzene, α-vinylbenzene, chloro-styrene or bromstyrol;

(d) vinyl ester, as vinyl-acetic ester, phenylformic acid vinyl ester, vinyl acetate base phenylester or Mono Chloro Acetic Acid vinyl ester;

(e) maleimide, as N-normal-butyl maleimide, N-tertiary butyl maleimide, N-sec.-propyl maleimide or N-cyclohexyl maleimide.

According to first embodiment, can a kind of compound of (methyl) acrylate will be selected from, or two or more compounds are as the main ingredient of polymerizable monomer composition.Be selected from the content of described a kind of compound of (methyl) acrylate, or the content of described two or more compounds preferably is not less than 50 weight % in the total amount of polymerisable compound, what more wish is to be not less than 60 weight %, what more wish is to be not less than 70 weight %, and it is desirable for all monomers that are included in the polymerizable monomer composition the most and all be selected from (methyl) acrylate.

According to first embodiment, with the compound of following described particular types during as doping agent, compare with the composition that does not contain this doping agent, the composition that comprises described doping agent has bigger specific refractory power, perhaps with the polymer phase ratio that does not contain as the doping agent of comonomer, the multipolymer that comprises as the doping agent of comonomer has bigger specific refractory power.Wish to use: the fluorizated polymerisable monomer of wherein being replaced, have at least a C-F key in the c h bond to the small part hydrogen atom by fluorine atom.Particularly, wish to use any compound that is selected from above-mentioned fluoridizing (methyl) acrylate, perhaps use wherein at least a be selected from above-mentioned fluoridizing (methyl) acrylate and fluorinated acrylic ester and at least a be selected from non--fluoridize any mixture of (methyl) acrylate.

In order further to reduce transmission loss, wish to use above-named monomeric deuterate compound.

The 1-1-2 polymerization starter

Described composition comprises the polymerization starter that can cause described polymerizable monomer composition polyreaction.According to various factors, as be included in polymerisable monomer or polymerization process in the composition, can from known polymerizable initiator, choose polymerization starter.The example of polymerization starter comprises: superoxide, as benzoyl peroxide (BPO), t-butyl peroxy-2-ethylhexanoate (PBO), ditertiary butyl peroxide (PBD), BPIC (t butyl peroxy isopropyl carbonate) (PBI) or normal-butyl-4,4-two (t-butyl peroxy) valerate (PHV); And azo-compound, as 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two (2-methylpropane), 2,2 '-azo two (2-methylbutane), 2,2 '-azo two (2-methylpentane), 2,2 '-azo two (2, the 3-dimethylbutane), 2,2 '-azo two (2-methyl hexane), 2,2 '-azo two (2,2,2 the 4-dimethylpentane), '-azo two (2,3, the 3-triptane), 2,2 '-azo two (2,4, the 4-trimethylpentane), 3,3 '-azo two (3-methylpentane), 3,3 '-azo two (3-methyl hexane), 3,3 '-azo two (3,3,3 the 4-dimethylpentane), '-azo two (3-ethylpentane), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), diethyl-2,2 '-azo two (methylpropionate), or di-t-butyl-2,2 '-azo two (2 Methylpropionic acid ester).

Also two or more polymerization starters can be used in combination in addition.

The 1-1-3 chain-transfer agent

According to first embodiment, described composition preferably comprises chain-transfer agent.Chain-transfer agent mainly can be used for regulating the molecular weight of the polymkeric substance that obtains.Can consider employed monomer and suitably select chain-transfer agent.The chain transfer constant that is used for various monomeric chain-transfer agents can be edited JOHNWILEY﹠amp with reference to following publication by J.BRANDRUP and E.H.IMMERGUT; " the polymer handbook third edition " that SON publishes.Chain transfer constant is property check acquisition by experiment also, described check (is write by Takayuki OhtsuandMasaetsu Kinoshita according to being disclosed in " method among the Kohbunshi gousei no jikkenhou (being used for polymkeric substance synthetic experimental technique) ", Kagaku-Dojin press publishes, INC (1972)) carry out.

When methyl methacrylate is used as polymerisable monomer, desirablely be, to be selected from alkyl sulfhydryl (just-butyl sulfhydryl, n-amyl mercaptan, n-octyl mercaptan, just-lauryl mercaptan, uncle-decyl mercaptan or the like) and thiophenol (thiophenol ,-the bromine thiophenol, right-the bromine thiophenol, between-thiocresol, right-thiocresol or the like) at least a as chain-transfer agent.Wherein, alkyl sulfhydryl, as n-octyl mercaptan, just-lauryl mercaptan or uncle's decyl mercaptan are preferred.In addition, when being replaced by D atom, the small part hydrogen atom also can use chain-transfer agent when c h bond.Also two or more chain-transfer agents can be used in combination in addition.

1-1-4 doping agent: specific refractory power toughener

Comprise according to the first embodiment polymerisable compound and to have the compound that is different from the polymerizable monomer component specific refractory power.Doping agent can be polymerisable or not polymerisable.When using the polymerizable doping agent, because the copolymerization of polymerizable monomer component and doping agent may take place, therefore with the various performances of more difficult adjusting, yet, but can obtain the such advantage of thermotolerance.In addition, doping agent is also referred to as the specific refractory power toughener, be a kind of compound of comparing with the composition that does not contain doping agent with the specific refractory power that increases the composition that comprises doping agent, the compound that perhaps has the specific refractory power that increases the multipolymer that contains doping agent (as the copolymerization component) with the polymer phase ratio that does not contain doping agent.Wish to be not less than 0.001 at composition that contains doping agent and the refringence that do not contain between the composition of doping agent.

According to first embodiment, at least a compound that is selected from the benzene derivative with phenyl ring is used as doping agent, described phenyl ring is replaced by at least one substituting group.The present inventor finds, exists negative related in substituent Hammett value and phenyl ring between the wavelength of the absorption peak of the 4th overtone of C-H stretching vibration.In other words, be subjected to owing to the absorption peak of the 4th overtone of C-H stretching vibration in the phenyl ring that the substituent of other carbon atom influences in this phenyl ring, and when substituent Hammett value more hour, the absorption peak of the 4th overtone of this stretching vibration will move to long wavelength's direction more.In order to reduce the transmission loss at 850nm wavelength place, preferably, make the absorption peak of the 4th overtone that belongs to the C-H stretching vibration migrate to more long wavelength, so that the root that makes absorption peak or absorption is away from 850nm.

In order to prevent that influence absorbs doping agent at the 850nm place, wish that the absorption peak of doping agent be not shorter than the 875nm place, what more wish is not to be shorter than the 877nm place, what more wish is not to be shorter than the 880nm place.When using when not being shorter than 880nm place and having the doping agent of absorption peak, because the transmission loss of transmission light due to the absorption of 850nm place can take place hardly.

For the absorption peak that makes the 4th overtone that belongs to the C-H stretching vibration migrates to more long wave strong point, a substituting group or a plurality of substituent Hammett value wish to be not more than 0.04, and what more wish is to be not more than-0.05, and what more wish is to be not more than-0.1.The minimum value of Hammett value wishes it is-0.6.In addition, by introducing a described substituting group or described a plurality of substituting group, the quantity of c h bond will reduce, and, as extra effect, will further reduce because the transmission loss due to the absorption of the 4th overtone of C-H self stretching vibration.

In this manual, when having substituting group, the Hammett value refers to the substituent Hammett constant described in the ChemicalReviews (the 91st volume, the 2nd, 168-175 page or leaf (1991)).When at ortho position and para-orientation, adopt identical Hammett constant usually, and when replacing, adopt different Hammett constants usually in position.For example, by the benzene compound of substituting group replacement, with respect to substituent R ¹The position, two hydrogen atoms are correspondingly arranged at the ortho position and a hydrogen atom are arranged in contraposition.Work as R ¹Be σ in contraposition and adjacent Hammett constant _1p, and R ¹At the Hammett of position constant is σ _1mThe time, Hammett value σ can calculate according to following formula:

σ＝(σ _1px3+σ _1mx2)/5

On the other hand, when having a plurality of substituting group, the Hammett value refers to the mean value of its Hammett value.When having a plurality of substituting group, the method for calculation of Hammett value will be that example is described hereinafter so that a phenyl ring and two phenyl ring to be arranged respectively.It is pointed out that when i is any positive number the R that replaces in a position ⁱThe Hammett constant be called σ _1m, and at substituted in the para or ortho position R ⁱThe Hammett constant be called σ _1p, in other words, the Hammett constant of contraposition also is used for the ortho position.

Method of calculation when having a phenyl ring:

In said structure, for each position a, b and c, substituent R ¹, R ²And R ³Hammett value summation be:

σ _a?＝σ _1p+σ _2m+σ _3m；

σ _b＝σ _1m+σ _2p+σ _3p；

σ _c＝σ _1m+σ _2p+σ _3p。

σ _a, σ _bAnd σ _cMean value, promptly the mean value of its summation of calculating according to following formula also is the mean value of a plurality of substituent Hammett value that has of above-claimed cpd.

σ＝(σ _a+σ _b+σ _c)/3

Method of calculation when having two benzene ring substitution groups:

In said structure, for each position a, b, c, d, e and f, substituent R ¹, R ², R ³, R ⁴With the Hammett value summation of-S-Ar group be:

σ _a＝σ _1p+σ _2m+σ _(sph)m；

σ _b＝σ _1m+σ _2p+σ _(sph)p；

σ _c＝σ _1m+σ _2p+σ _(sph)p；

σ _d＝σ _3m+σ _4p+σ _(sph)p；

σ _e＝σ _3p+σ _4m+σ _(sph)m；

σ _f＝σ _1m+σ _2p+σ _(sph)p；

It is pointed out that-the Hammett constant of S-Ph, i.e. σ _{(sph) m}Or σ _{(sph) p}Be used for-during S-Ar, will own-S-Ar is thought of as-S-Ph; Wherein Ph represents unsubstituted phenyl ring, and Ar represents the phenyl that replaces.

σ _a-σ _fMean value, promptly the mean value of its summation of calculating according to following formula is the mean value of a plurality of substituent Hammett value that has of above-claimed cpd.

σ＝(σ _a+σ _b+σ _c+σ _d+σ _e+σ _f)/6

Enumerated at this: the example of the benzene derivative that the Hammett value is not more than 0.04, replaced by a substituting group or a plurality of substituting group.

Hammett??σ＝-0.51????σ＝-0.07??????????σ＝-0.16???????????σ＝-0.11?????????????σ＝0.018

Value (1) (2) (3) (4) (5)

σ＝-0.35????????????σ＝-0.29?????????σ＝-0.59????????????????σ＝-0.30???????????σ＝-0.56

(6)????????????????????(7)?????????????(8)?????????????????????(9)????????????????????(10)

Be not more than 0.04 in the Hammett value, have in the compound of the phenyl ring that is replaced by a substituting group or a plurality of substituting group, its specific refractory power is equal to or greater than the specific refractory power of deuterate bromobenzene d-5, and promptly 1.56.Below the example that satisfies the compound of these conditions is listed in, but be not limited thereto.

σ＝0.03 ^*????????????????σ＝0.015???????????????????σ＝-0.073???????????????σ＝-0.117

(11)??????????????????????(12)?????????????????????????(13)?????????????????????(14)

σ＝-0.058?????????????????σ＝-0.28?????????????????σ＝-0.32????????????????σ＝-0.41

(15)???????????????????????(16)???????????????????????(17)?????????????????????(18)

σ＝-0.27?????????????????σ＝-0.117?????????????????σ＝-0.117????????????????σ＝-0.097

(19)??????????????????????(20)???????????????????????(21)???????????????????????(22)

σ＝-0.285??????????????σ＝-0.105???????????????σ＝-0.105???????????????σ＝-0.105

(23)????????????????????(24)?????????????????????(25)?????????????????????(26)

σ＝-0.15??????????????σ＝-0.17?????????????????σ＝-0.59???????????????????σ＝-0.158

(27)?????????????????????(28)????????????????????(29)????????????????????????(30)

σ＝-0.11??????????????????????σ＝-0.1?????????????????????????σ＝-0.033

(31)???????????????????????????(32)?????????????????????????????(33)

According to first embodiment, desirable is that doping agent is selected from the compound of being represented and satisfied above-mentioned condition by following structural formula (1).

Structural formula (1)

In structural formula (1), R ¹-R ¹⁰Represent hydrogen atom separately, alkyl, thiazolinyl, alkoxyl group, alkene oxygen base, or dialkylamino, precondition is wherein to represent alkyl, thiazolinyl, alkoxyl group, alkene oxygen base or dialkylamino at least four.

Can be with a kind of doping agent, perhaps two or more doping agents are used for polymerisable compound of the present invention.Must be selected from as all compounds of doping agent: compound with phenyl ring of a plurality of substituting groups replacements that are not more than substituting group of 0.04 by Hammett value or are not more than 0.04 by Hammett value mean value.

Optical component with gradation refractive index can prepare by the concentration graded that makes doping agent when the polymerisable compound polymerization of first embodiment.Making a kind of useful method of concentration of dopant fractionated is described subsequently interface gel polymerization method.

The preferred amount ranges of various components can suitably be determined according to the kind that is adopted, wherein, with respect to polymerizable monomer component, the addition of polymerization starter is wished in the scope of 0.005-0.5 weight %, more preferably in the scope of 0.010-0.50 weight %; And with respect to polymerizable monomer component, the addition of chain-transfer agent is wished in the scope of 0.10-0.40 weight %, more preferably in the scope of 0.15-0.30 weight %.With respect to polymerizable monomer component, the addition of doping agent is wished in the scope of 1-30 weight %, more preferably in the scope of 1-25 weight %.

It is pointed out that when the addition of doping agent increased, along with the decline of glass transition point Tg, thermotolerance descended during use, added the thermoplasticity of the polymkeric substance of doping agent and will improve easily.Therefore, preferably can obtain the doping agent of wishing the distribution specific refractory power with less amount.

Another possible strategy relates to: with the degree that does not reduce the light transmission performance other additive is added in the polymerisable compound.For example, additive can be added so that improve weathering resistance or wearing quality.In addition, can also add the emission inductive material of amplifying optical signals, so that improve the light transmission performance.Because even the optical signal of decay also can amplify by adding described compound, prolongs transmission length thus, therefore, described compound can be used to produce in light transmission connection section office fiber amplifier usually.

When heat and/or optical radiation are to polymerisable compound, produce radical etc. by initiator, make the polymerisable monomer polymerization reaction take place thus.Because the polymerisable compound according to first embodiment comprises doping agent, therefore, react the direction of carrying out by controlled polymerization, normally pass through described interface gel polymerization method subsequently, so that produce the concentration gradient of doping agent, perhaps produce the copolymerization ratio gradient of doping agent and polymerisable monomer, thereby can obtain refractive index distribution structure.According to first embodiment, for the inhalation effects light source that prevents the 4th overtone of C-H stretching vibration in the phenyl ring light, improve doping agent at 850nm, obviously migrate to more long wavelength so that absorb, therefore, because the transmission loss that doping agent causes is minimized.By between using or the polymerization starter or the chain-transfer agent that are added in the composition regulate the rate of polymerization and/or the polymerization degree, can obtain to have the polymkeric substance of wishing molecular weight.When use contains the polymerisable compound of chain-transfer agent, can come the molecular weight of telomerized polymer by chain-transfer agent, so that make it to have the tensile of being suitable for mechanical property.Therefore, when optical fiber is when preparing by the preformed articles of being produced by the polymerization of described composition is stretched, utilize such composition can also improve throughput.

Polyreaction by polymerisable compound of the present invention can prepare optical component, and described member comprises polymeric constituent and doping agent and has distribution specific refractory power based on dopant-concentration profile.Because the absorption peak of the 4th overtone of C-H stretching vibration is being not less than the 875nm place in the phenyl ring of doping agent, therefore, the transmission loss that is caused by doping agent will obviously reduce.Desirable is that doping agent is selected from said structure formula (1).Desirablely be to be included in homopolymer and multipolymer that polymkeric substance in the polymeric constituent is selected from (methyl) acrylate.

Second embodiment of 1-2 polymerisable compound

Second embodiment of polymerisable compound can be used to prepare the optical component that is used for the 850nm optical source wavelength.This polymerisable compound mainly comprises: polymerizable monomer component, and can cause its polymeric polymerization starter, and have the compound of different refractivity with monomer component, be also referred to as " doping agent " or " specific refractory power toughener " hereinafter sometimes.According to this second embodiment, by utilizing such compound as doping agent, described compound has at least one by the phenyl ring of a substituting group replacement or the replacement of a plurality of substituting group, a described substituent Hammett value is in a specified range, the mean value of described its Hammett value of a plurality of substituting group can reduce because the transmission loss that doping agent causes in described specified range.In addition, consider the consistency with fertile material, by further selecting the compound of solubility parameter in specified range for use, the transmission loss of the optical component of being produced by the polymerization of described composition can be reduced to lower level.The polymerisable compound of second embodiment can be used for producing optical component, particularly has the optical component that refractive index value distributes.Use description to the various materials of second embodiment below.

The 1-2-1 polymerizable monomer component

According to second embodiment, wish that polymerizable monomer component comprises at least a monomer that is selected from the ester of acrylic acid ester and its derivative that accounts for major portion.The example of the ester of vinylformic acid and derivative thereof comprises acrylate and methacrylic ester, and it all is called " (methyl) acrylate " hereinafter.Term " comprises the monomer that accounts for major portion " and not only refers to the embodiment of being made up of this monomer, but also refers to also comprise at least a embodiment that is different from described monomeric polymerisable monomer, only otherwise can reduce optical characteristics.For example, composition can comprise at least a monomer that is selected from except that (methyl) acrylate, and for example vinylbenzene or maleimide are so that form multipolymer.According to second embodiment, particularly consider water-fast-heat-stable performance, preferred alicyclic (methyl) acrylate that uses by structural formula (2) expression.

Structural formula (2)

In this structural formula, X ¹Be hydrogen (H) or deuterium (D), wherein two X ¹Can be identical or different; Y ¹Expression H, D, CH ₃Or CD ₃R ¹Expression C _7-20Alicyclic hydrocarbon.

Polymerisable monomer by structural formula (2) expression is: have C _7-20(methyl) acrylate derivative of alicyclic hydrocarbon radical.The example of polymerisable monomer comprises: two ring [2.2.1] heptyl-2 (methyl) acrylate, (methyl) vinylformic acid 1-adamantane esters, (methyl) vinylformic acid 2-adamantane esters, (methyl) vinylformic acid 3-methyl isophthalic acid-adamantane esters, (methyl) vinylformic acid 3,5-dimethyl-1-adamantane esters, (methyl) vinylformic acid 3-ethyl adamantane esters, (methyl) vinylformic acid 3-methyl-5-ethyl-1-adamantane esters, (methyl) vinylformic acid 3,5,8-triethyl-1-adamantane esters, (methyl) vinylformic acid 3,5-dimethyl-8-ethyl-1-adamantane esters, (methyl) vinylformic acid octahydro-4,7-menthanoindene-5-il ester, (methyl) vinylformic acid octahydro-4, the 7-menthanoidene-1-yl methyl ester, (methyl) vinylformic acid three ring decyl ester, (methyl) vinylformic acid 3-hydroxyl-2,6,6-trimethylammonium-two ring [3.1.1] heptyl ester, (methyl) vinylformic acid 3,7,7-trimethylammonium-4-hydroxyl-two ring [4.1.0] heptyl ester, (methyl) vinylformic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid phenyl (phentyl) ester and (methyl) vinylformic acid 2,2,5-3-methyl cyclohexanol ester.Wherein, (methyl) vinylformic acid norbornene ester, (methyl) isobornyl acrylate and (methyl) phenyl acrylate are preferred, more preferably (methyl) vinylformic acid norbornene ester and (methyl) isobornyl acrylate.

According to second embodiment, preferably will be selected from two or more compounds of comprising (methyl) acrylatcs systems as the main ingredient in the polymerizable monomer component.With respect to the gross weight meter of polymerizable monomer component, by the content of at least a compound of structural formula (2) expression preferably from 5-95 weight %, more preferably from 10-95 weight %, more preferably from 10-90 weight %.Consider and to carry out the compensation of fragility and mechanical property to the compound of structural formula (2) expression, other preferred example that can be used as (methyl) acrylate of polymerisable monomer comprises: methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic acid isopropyl esters, the methacrylic tert-butyl acrylate, the methacrylic acid benzylester, methacrylic acid phenylester, cyclohexyl methacrylate, methyl acrylate, ethyl propenoate, n-butyl acrylate, tert-butyl acrylate and phenyl acrylate.What wherein, wish most is methyl methacrylate.

When being used in combination when at least a compound that will be selected from structural formula (2) with as the methyl methacrylate of other polymerisable monomer, in order to guarantee enough hydrophobicitys, preferably, gross weight with respect to polymerisable monomer, the content that is selected from least a compound of structural formula (2) is not less than 10 weight %, more preferably is not less than 15 weight %.When the polymerisable monomer that uses except that methyl methacrylate, also in described scope.

At least a monomer except that (methyl) acrylate also can be used for second embodiment.Other example that can be used for the polymerisable monomer in second embodiment is listed below, but is not limited thereto.

(d) vinyl ester, as vinyl-acetic ester, phenylformic acid vinyl ester, vinyl acetate base phenylester or Mono Chloro Acetic Acid vinyl ester; With

According to the present invention, when at least two kinds of compounds that are selected from (methyl) acrylate during as the main ingredient of polymerizable monomer component, the total content of described (methyl) acrylate preferably is not less than 50 weight % in the total amount of polymerizable monomer component, what more wish is to be not less than 60 weight %, what more wish is less than 70 weight %, and that wish the most is 100 weight %.

According to second embodiment, with the compound of following described particular types during as doping agent, compare with the composition that does not contain this doping agent, the composition that comprises described doping agent has bigger specific refractory power, perhaps with the polymer phase ratio that does not contain as the doping agent of comonomer, the multipolymer that comprises as the doping agent of comonomer has bigger specific refractory power.Being included in c h bond in the polymerisable monomer can increase the transmission loss of optical component, especially at 850nm optical source wavelength place, therefore, more it is desirable for the deuterate polymerisable monomer that use comprises a C-D key at least.

The 1-2-2 polymerization starter

Described composition comprises: the polymerization starter that can cause described polymerizable monomer composition polyreaction.According to various factors, as be included in polymerisable monomer or polymerization process in the composition, can from known polymerizable initiator, choose polymerization starter.The example of polymerization starter comprises: superoxide, as benzoyl peroxide (BPO), t-butylperoxy-2-ethylhexanoate (PBO), ditertiary butyl peroxide (PBD), BPIC (t butyl peroxy isopropyl carbonate) (PBI) or normal-butyl-4,4-two (t-butyl peroxy) valerate (PHV); And azo-compound, as 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo (hexanaphthene-1-nitrile), 2,2 '-azo two (2-methylpropane), 2,2 '-azo two (2-methylbutane), 2,2 '-azo two (2-methylpentane), 2,2 '-azo two (2, the 3-dimethylbutane), 2,2 '-azo two (2-methyl hexane), 2,2 '-azo two (2, the 4-dimethylpentane), 2,2 '-azo two (2,3, the 3-triptane), 2,2 '-azo two (2,4,3,3 the 4-trimethylpentane), '-azo two (3-methylpentane), 3,3 '-azo two (3-methyl hexane), 3,3 '-azo two (3, the 4-dimethylpentane), 3,3 '-azo two (3-ethylpentane), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), diethyl-2,2 '-azo two (2 Methylpropionic acid ester) or di-t-butyl-2,2 '-azo two (2 Methylpropionic acid ester).Also two or more polymerization starters can be used in combination in addition.

The 1-2-3 chain-transfer agent

Composition according to second embodiment can comprise chain-transfer agent.Chain-transfer agent mainly can be used for regulating the molecular weight of the polymkeric substance that obtains.Can consider employed monomer and suitably select chain-transfer agent.The chain transfer constant that is used for various monomeric chain-transfer agents can be edited JOHN WILEY﹠amp with reference to following publication by J.BRANDRUP and E.H.IMMERGUT; SON publishes " the polymer handbook third edition ".Chain transfer constant is property check acquisition by experiment also, described check (is write by Takayuki Ohtsu and Masaetsu Kinoshita according to being disclosed in " method among the Kohbunshi gousei no jikkenhou (being used for polymkeric substance synthetic experimental technique) ", Kagaku-Dojin press publishes, INC (1972)) carry out.

When methyl methacrylate is used as polymerisable monomer, desirablely be, to be selected from alkyl sulfhydryl (just-butyl sulfhydryl, n-amyl mercaptan, n-octyl mercaptan, just-lauryl mercaptan, uncle-decyl mercaptan or the like) and thiophenol (thiophenol ,-the bromine thiophenol, right-the bromine thiophenol, between-thiocresol, right-thiocresol or the like) at least a as chain-transfer agent.Wherein, alkyl sulfhydryl, as n-octyl mercaptan, just-lauryl mercaptan or uncle's decyl mercaptan are preferred.When being replaced by D atom, the small part hydrogen atom also can use chain-transfer agent when c h bond wherein in addition.Also two or more chain-transfer agents can be used in combination in addition.

1-2-4 doping agent: specific refractory power toughener

According to second embodiment, polymerisable compound comprises and has the compound that is different from the polymerizable monomer component specific refractory power.Doping agent can be polymerisable or not-polymerisable.When using the polymerizable doping agent, because the copolymerization of polymerizable monomer component and doping agent may take place, therefore with the various performances of more difficult adjusting, yet, but can obtain the such advantage of thermotolerance.In addition, doping agent is also referred to as the specific refractory power toughener, be a kind of compound of comparing with the composition that does not contain doping agent with the specific refractory power that increases the composition that comprises doping agent, the compound that perhaps has the specific refractory power that increases the multipolymer that contains doping agent (as the copolymerization component) with the polymer phase ratio that does not contain doping agent.Wish to be not less than 0.001 at composition that contains doping agent and the refringence that do not contain between the composition of doping agent.

According to second embodiment, at least a compound that is selected from the benzene derivative with phenyl ring is used as doping agent, described phenyl ring is replaced by at least one substituting group.The present inventor finds, exists negative related in substituent Hammett value and phenyl ring between the wavelength of the absorption peak of the 4th overtone of C-H stretching vibration.In other words, be subjected to owing to the absorption peak of the 4th overtone of C-H stretching vibration in the phenyl ring that the substituent of other carbon atom influences in this phenyl ring, and when substituent Hammett value more hour, the absorption peak of the 4th overtone of this stretching vibration will move to long wavelength's direction more.In order to be reduced in the transmission loss at 850nm wavelength place, preferably, make the absorption peak that belongs to C-H stretching vibration the 4th overtone migrate to more long wavelength, so that the root that makes absorption peak or absorption is away from 850nm.

In order to prevent that influence absorbs doping agent at the 850nm place, wish that the absorption peak of doping agent be not shorter than the 875nm place, what more wish is not to be shorter than the 877nm place, what more wish is not to be shorter than the 880nm place.When using absorption peak when not being shorter than the doping agent at 880nm place, because the transmission loss of transmission light due to the absorption of 850nm place can take place hardly.

In order to make the absorption peak that belongs to C-H stretching vibration the 4th overtone migrate to more long wave strong point, a substituting group or a plurality of substituent Hammett value wish to be not more than 0.04, and what more wish is to be not more than-0.05, and what more wish is to be not more than-0.1.The minimum value of Hammett value wishes it is-0.6.In addition, by introducing a described substituting group or described a plurality of substituting group, the quantity of c h bond will reduce, and, as extra effect, will further reduce because the transmission loss due to the absorption of the 4th overtone of C-H self stretching vibration.

σ＝(σ _1px3+σ _1mx2)/5

Method of calculation when having a phenyl ring:

σ _a＝σ _1p+σ _2m+σ _3m；

σ _b＝σ _1m+σ _2p+σ _3p；

σ _c＝σ _1m+σ _2p+σ _3p；

σ _a, σ _bAnd σ _cMean value, promptly the mean value of its summation of calculating according to following formula also is the mean value of a plurality of substituent Hammett value that above-claimed cpd had.

σ＝(σ _a+σ _b+σ _c)/3

Method of calculation when having a plurality of substituting group:

σ _a＝σ _1p+σ _2m+σ _(sph)m；

σ _b＝σ _1m+σ _2p+σ _(sph)p；

σ _c＝σ _1m+σ _2p+σ _(sph)p；

σ _d＝σ _3m+σ _4p+σ _(sph)p；

σ _e＝σ _3p+σ _4m+σ _(sph)m；

σ _f＝σ _1m+σ _2p+σ _(sph)p；

σ＝(σ _a+σ _b+σ _c+σ _d+σ _e+σ _f)/6

In addition, the fertile material that is used in combination and the consistency of doping agent equally also have tangible influence to transmission loss.As mentioned above, have enough hydrophobic fertile material and have good water-fast-Re patience and favorable mechanical performance simultaneously.Be the doping agent that acquisition has excellent compatibility, the present inventor has carried out various researchs, found that, solubility parameter (SP) is not more than 10.9,

Preferably be not more than 10.8, the benzene derivative more preferably no more than 10.6 has good consistency, and by using such compound, can obtain to have the optical component of good transparency and low transmission loss.Have by substituting group replaces or a plurality of substituting group replaces phenyl ring, Hammett value be not more than 0.04 and the SP value to be not more than the example of 10.9 doping agent as follows, but be not limited thereto.It is pointed out that the SP value calculates according to the Fedors method that is described in " PolymerEngineering and Science " (14th volume, 147-154 page or leaf).

σ＝0.03 ^*????????????????σ＝0.015????????????????????σ＝-0073??????????????σ＝-0.117

SP value 10.7 SP values 10.7 SP values 10.4 SP values 10.4

2-(1)?????????????????????2-(2)????????????????????????2-(3)??????????????????2-(4)

σ＝-0.058???????????????σ＝-0.28??????????????????σ＝-0.32???????????????σ＝-0.41

SP value 10.3 SP values 10.3 SP values 10.2 SP values 10.1

2-(5)????????????????????2-(6)??????????????????????2-(7)???????????????????2-(8)

σ＝-0.27????????????????σ＝-0.117????????????????σ＝-0.117???????????????σ＝-0.097

SP value 10.4 SP values 10.4 SP values 10.4 SP values 10.4

2-(9)????????????????????2-(10)?????????????????????2-(11)???????????????????2-(12)

σ＝-0.285???????????????σ＝-0.105????????????????σ＝-0.105???????????????????σ＝-0.15

SP value 10.5 SP values 9.1 SP values 10.6 SP values 10.7

2-(13)????????????????????2-(14)???????????????????2-(15)????????????????????????2-(16)

σ＝-0.59???????????????????σ＝-0.158

SP value 10.4 SP values 10.7

2-(17)??????????????????????2-(18)

Can be with a kind of doping agent, perhaps two or more doping agents are used for the polymerizable components of second embodiment.Must be selected from as all compounds of doping agent: phenyl ring and SP value with a plurality of substituting groups replacements that are not more than substituting group of 0.04 by Hammett value or are not more than 0.04 by Hammett value mean value are not more than 10.9 compound.

Change the preferred addition of doping agent according to the ability that increases specific refractory power and with the interaction of polymeric matrix.Usually, with respect to the total amount of polymerisable compound, the addition of doping agent is preferably in the scope of 1-30 weight %, more preferably in the scope of 3-25 weight %, more preferably in the scope of 5-20 weight %.

The preferred amount ranges of various components can suitably be determined according to the kind that is adopted, wherein, with respect to polymerizable monomer component, the addition of polymerization starter is wished in the scope of 0.005-0.5 weight %, more preferably in the scope of 0.010-0.50 weight %; And the addition of chain-transfer agent is wished in the scope of 0.10-0.40 weight %, more preferably in the scope of 0.15-0.30 weight %.With respect to polymerizable monomer component, the addition of doping agent is wished in the scope of 1-30 weight %, more preferably in the scope of 1-25 weight %.

When heat and/or optical radiation are to polymerisable compound, produce radical etc. by the polymerizable initiator, make at least a polymerisable monomer polymerization reaction take place thus.Because the polymerisable compound according to second embodiment comprises doping agent, therefore, react the direction of carrying out by controlled polymerization, normally pass through described interface gel polymerization method subsequently, so that produce the concentration gradient of doping agent, perhaps produce the copolymerization ratio gradient of doping agent and at least a polymerisable monomer, thereby can obtain the specific refractory power hierarchy.According to second embodiment, for the inhalation effects light source that prevents the 4th overtone of C-H stretching vibration in the phenyl ring light at the 850nm place, improve doping agent, obviously migrate to more long wavelength so that absorb, therefore, the transmission loss that causes owing to doping agent is minimized.In addition, consider and have enough consistencies of hydrophobic polymeric matrix,, will further reduce transmission loss and improve water-fast-thermotolerance by utilizing the doping agent of SP value in specified range.By between using or the polymerization starter or the chain-transfer agent that are added in the composition regulate the rate of polymerization and/or the polymerization degree, can obtain to have the polymkeric substance of wishing molecular weight.When use contains the polymerisable compound of chain-transfer agent, can come the molecular weight of telomerized polymer by chain-transfer agent, so that make it to have the tensile of being suitable for mechanical property.Therefore, when optical fiber is to stretch when preparing by the preformed articles that the polymerization of described composition is produced, utilize such composition can also improve throughput.

2. optical component

To describe the method for the polymerisable compound production optical component that utilizes first or second embodiment below for example in detail.Example described below is: wherein the polymerisable compound of first or second embodiment is used to produce the example in the core district of the gradation refractive index optical component that comprises core district and clad region.

GI type optical component can be produced by the following method: (1) is equivalent to the hollow structure (for example, right cylinder) of clad region by the polyreaction preparation of polymerisable compound; (2) prepare by the polymerisable compound polymerization that in the hollow space of described structure, makes first or second embodiment and comprise the preformed articles that is equivalent to core district and clad region respectively; (3) preformed articles that is obtained is processed into various forms.

By the hollow structure (for example right cylinder) of the first step acquisition by polymer.As described in the open WO93/08488 of international monopoly, polymerisable compound is poured in the right cylinder polymerization container, rotary container (preferably making cylinder axis maintenance level) carries out polymerization then, is called " rotation polymerization " herein after reaching, and forms the right cylinder of being made up of polymkeric substance thus.Can be with at least a polymerization starter, at least a transfer agent and at least a if necessary additive such as stablizer are poured in the container that contains a kind of polymerisable monomer at least.Suitable polymerization temperature and cycle can change according to the monomeric kind of use.Usually, preferably at 60-90 ℃ of polymerization 5-24 hour.Can before polymerization, carry out prepolymerization at this employed monomer, so that increase viscosity thus, described in JPA No.1996-110419 (term " JPA " is not examined disclosed Japanese patent application in this expression).Because the hollow structure that rotation is obtained in the time of may being out of shape may be out of shape, therefore, the preferred use has enough inflexible metals or Glass Containers when container.

The main component of the polymerizable monomer composition of using in first step is preferably identical with the main component of the polymerizable monomer composition used in second step.Its quantitative and less composition can be identical or different.

When the polymerisable compound of first embodiment is used for second step, for using the polymerisable monomer that in first step, is used to form clad region to have no particular limits.Its example comprises: (methyl) acrylate, and as methyl methacrylate, methacrylic tert-butyl acrylate, methacrylic acid cyclohexyl ester, methacrylic acid three ring [5.2.1.0 ^2,6] decyl ester, methacrylic acid adamantane esters, IBOMA; And fluorizated (methyl) acrylate, as methacrylic acid 2,2,2-trifluoroethyl ester, methacrylic acid 2,2,3,3-tetrafluoro propyl diester, methacrylic acid 2,2,3,3,3-five fluoropropyl esters, methacrylic acid 1-trifluoromethyl-2,2,2-trifluoroethyl ester, methacrylic acid 2,2,3,3,4,4,5,5-octafluoro amyl group ester or methacrylic acid 2,2,3,3,4,4-hexafluoro butyl ester.A kind of polymerisable monomer or two or more polymerisable monomers can be used for first step.When using two or more polymerisable monomers, the ratio of its hope can change according to the kind of polymerisable monomer.

When the polymerisable compound of second embodiment is used for second step, for using the polymerisable monomer that in first step, is used to form clad region to have no particular limits.Its spendable example is with above-named identical.Desirable is that at least a compound that will be selected from structural formula (2) is used for first step.

The other material that is used for first step such as polymerization starter or chain-transfer agent are had no particular limits, and can from various known materials, select according to employed polymerisable monomer.Described examples of material be used for cited identical of first or second polymerisable compound.Usually, the preferred addition of polymerization starter is the 0.1-1.00 weight % of amount of monomer, more preferably 0.40-0.60 weight %; And the preferred addition of chain-transfer agent is the 0.10-0.40 weight % of amount of monomer, more preferably 0.15-0.30 weight %.

Described hollow circular cylinder preferably has a bottom, can pour right cylinder into so that be used for the material in core district in second step.The preferred material that is used for the bottom is with cylindrical polymkeric substance good affinity and adhesive material to be arranged.Described bottom can be by the polymer formation identical with right cylinder.For example, described bottom can be by pouring small amounts of monomer in the container into before or after the rotation polymerization; And be kept upright at container and make monomer polymerization under static and prepare formation.

In order to make residual monomer or residue polymerization starter complete reaction, after described rotation polymerization, can heat-treat being higher than under the temperature of polymerization temperature, perhaps remove unpolymerized component.

In first step, by utilizing known molding technology such as extrusion molding polymkeric substance is carried out molding, also may produce and have desirable shape the structure of (in the present embodiment, being right cylinder).

When producing cylindrical structure by molding and the polymerisable compound of second embodiment is used for second step, the example of spendable polymkeric substance comprises: by the polymkeric substance that the second polymerisable compound polymerization is produced, but do not comprise any doping agent; Poly(vinylidene fluoride), fluorizated (methyl) acrylate based polyalcohol and amorphous polyolefin.The specific refractory power of fluorinated polymer is usually less than non--fluorinated polymer, and utilizes such fluorinated polymer, and hole count will increase; Yet the tackiness to the core district descends sometimes.In this case, for guaranteeing enough tackinesss,, can between core district and clad region, form the outer core district by the polymerization of (not comprising any doping agent) of second polymerisable compound.Clad region and outer core district can produce simultaneously by molding technology such as co-extrusion molding.

In second step, pour the polymerisable compound of first or second embodiment into the cylindrical hollow space that obtains by first step, to be equivalent to clad region, make monomer carry out polymerization then.When forming the outer core district, polymerizable monomer composition is poured in the double-deck cylindrical hollow space.Consider the residuum after the polyreaction, preferably carry out polymerization by the method based on the interface gel polymerization process, described polymerization process does not have solvent, and it is disclosed among the open WO93/08488 of international monopoly.In the interface gel polymerization process, the polymerization of polymerisable monomer radially begins to carry out from its inwall along cylindrical and since gel effect towards the center its viscosity higher.When use contains the polymerisable compound of doping agent in polymerization, at first, have more first mainly being present on the right cylinder inwall of monomer of high affinity with cylindrical polymkeric substance, and then carry out polymerization, so that on circumferential periphery, produce polymkeric substance with more low-doped agent content.In the polymkeric substance that next generates, the ratio of doping agent will increase towards the person center.The distribution that this has successfully realized the concentration distribution of doping agent and therefore introduced specific refractory power in the zone that is equivalent to the core district.And, when doping agent has polymerizable groups and cylindrical polymkeric substance have more that the monomer of high affinity mainly is present on the right cylinder inwall, and then carry out polymerization, so that form polymkeric substance in the periphery with more low-doped dose of copolymerization share.In the polymkeric substance that next generates, the copolymerization ratio of doping agent will increase towards the center.This copolymerization ratio that has successfully realized doping agent distributes, and has therefore introduced the distribution based on the specific refractory power of classification copolymerization ratio in the zone that is equivalent to the core district.

By second step, not only index distribution has been introduced in the zone that is equivalent to the core district, and, because it is also different to have the thermal characteristics in different refractivity zone, therefore also introduced the distribution of thermal characteristics.If the polyreaction in second step is carried out under constant temperature, response performance with respect to volumetric shrinkage in polyreaction can change according to thermal characteristics, in the preformed articles that obtains, may produce bubble or microfracture thus, and in the fiber that may cause being obtained of the stretching under the described preformed articles of heating numerous air-bubble be arranged.If the polyreaction of second step is carried out under too low temperature, because low polymerization efficiency, throughput may be quite low, and perhaps the optical transmission performance of resultant optical component may be owing to polymerization not exclusively reduces.On the contrary, if the polyreaction of second step is carried out under too high initial polymerization temperature, initial polymerization speed may be too fast, thereby the volumetric shrinkage in core district can not relax by loose response, and the result is to produce numerous air-bubble in the core district.Therefore, preferably carry out polyreaction in suitable temperature.When methacrylic ester commonly used was used as monomer, described polyreaction was more preferably carried out under 80-120 ℃ temperature preferably at 50-150 ℃.In order to improve the response performance in polyreaction, also preferably under the inert gas atmosphere of pressurization, carry out polymerization with respect to volumetric shrinkage.By the dehydration or the degassing, might further reduce the degree that produces bubble.

(1) utilize first polymerisable compound:

Preferred polymerization temperature and polymerizable time change according to employed polymerisable monomer.Usually, polymerization temperature is wished at 60-90 ℃, and polymerization time was wished at 5-24 hour.Also it is desirable for the polymerization starter that uses its 10 hour transformation period decomposition temperature to be lower than the polymerisable monomer boiling point in addition, and 25% o'clock of polymerization starter transformation period of being aggregated in of polymerisable monomer is carried out.When under described condition, carrying out polymerization, might reduce initial polymerization speed, improve response performance, and therefore reduce, and improve throughput because volumetric shrinkage produces the degree of bubble in preformed articles with respect to volumetric shrinkage.The 10 hour transformation period decomposition temperature that it is pointed out that polymerization starter refers to: polymerization starter decomposes the temperature when being reduced to half amount in 10 hours.When methyl methacrylate (MMA) is used as polymerisable monomer, can from above-mentioned listed polymerization starter, select 10 hour transformation period decomposition temperature be not less than 2,2 of MMA boiling point '-azo two (2-methylpropane) or 2,2 '-azo two (2,4, the 4-trimethylpentane).When MMA is used as polymerization starter as polymerisable monomer and with the latter, preferably, keep the initial polymerization temperature that polymerization was carried out 48-72 hour, can also carry out 24-48 hour polymerization rising under 120-140 ℃ the temperature then.When with the former when the polymerization starter, preferably, keeping the initial polymerization temperature that polymerization was carried out 4-24 hour, can also carry out 24-48 hour polymerization rising under 120-140 ℃ the temperature then.Can progressively heat up or heat up continuously, wherein preferred short mode of heating-up time.

(2) when using second polymerisable compound:

At least comprise by the preferred polymerizing condition of alicyclic (methyl) acrylate-based monomeric second polymerisable compound of structural formula (2) expression identical with the polymerizing condition of the polymerisable compound that comprises common (methyl) acrylate.Therefore, described polyreaction is more preferably carried out under 80-120 ℃ temperature preferably at 50-150 ℃.In order to improve in polyreaction response performance, also preferably under the inert gas atmosphere of pressurization, carry out polymerization with respect to volumetric shrinkage.Preferably, keep the initial polymerization temperature that polymerization was carried out 4-24 hour, can also carry out 24-48 hour polymerization rising under 120-140 ℃ the temperature then.Polymerization starter can be selected according to polymerization temperature or polymerization time.When carrying out polyreaction under these conditions, polymerization starter is preferably selected from pyrolytic decomposition type initiator, as ditertiary butyl peroxide (PBD) or 2,2 '-azo two (2,4, the 4-trimethylpentane).Can progressively heat up or heat up continuously, wherein preferred short mode of heating-up time.

In second step, preferably carry out polyreaction (being called " pressure polymerization " subsequently) adding to depress.Under the situation of pressure polymerization, preferably right cylinder is placed the vacancy of anchor clamps, carry out polyreaction when keeping right cylinder by fixture supports.When the hollow space that is equivalent to the clad region structure carries out pressure polymerization, make this structure keep being inserted in vacancy in the anchor clamps, anchor clamps will prevent because pressure causes structural distortion like this.Anchor clamps preferably have the hollow space that wherein can insert described structure, and described hollow space preferably has the profile that is similar to described structure.Be shaped with right cylinder owing to be equivalent to the structure of clad region in the present embodiment, therefore, further preferably described anchor clamps are cylindrical.Anchor clamps can stop cylindrical distortion during pressure polymerization, and supporting cylinder, so that the contraction that is equivalent to the core area along with making of pressure polymerization is alleviated.Preferably, the diameter of described anchor clamps hollow space is greater than individual layer or double-deck cylindrical external diameter, and described anchor clamps are equivalent to the right cylinder of clad region with non-adhesion system supporting.Because anchor clamps are cylindrical in the present embodiment, therefore, the internal diameter of anchor clamps is preferably than the big 0.1-40% of cylindrical external diameter that is equivalent to clad region, more preferably big 10-20%.

When being inserted the anchor clamps hollow space, right cylinder right cylinder can be placed aggregation container.In aggregation container, preferably, described right cylinder is placed, so that can vertically calibrate its short transverse.In by fixture supports, right cylinder is placed after the aggregation container, aggregation container is pressurizeed.Preferably, utilize rare gas element such as nitrogen that aggregation container is pressurizeed, and therefore pressure polymerization also preferably carry out under inert gas atmosphere.The preferred pressure scope can change according to monomeric kind between polymerization period, usually at about 0.05-1.0MPa.

Can obtain to be used for the preformed articles of plastic optics member by first and second steps.

In third step, by the preformed articles of being produced by above-mentioned steps is carried out the optical component that processing treatment can obtain to wish.For example, will obtain the planar lenses of plate shape or cylindricality to the cutting of preformed articles, fusion drawn will obtain plastic optical fiber.

Can produce optical fiber by adding thermal stretch in the third step.Suitable Heating temperature during can determining to stretch according to the source material of preformed articles, usually preferred Heating temperature scope is at 180-250 ℃.Suitable stretching condition (draft temperature or the like) can be determined according to the diameter of acquisition preformed articles, diameter and the employed source material that plastic optical fiber is wished.Particularly for the optical fiber with gradation refractive index, should stretch equably wire drawing and heating are so that destroy the distribution of the specific refractory power that radially changes.Therefore, preferably, utilization can be heated preformed articles at the cylindrical heater of its cross-wise direction even heating, and utilizes the stretching drawing apparatus that preformed articles is drawn into fiber, and described device has the central position of making constant correcting mechanism.For molten plastic is orientated, described in JPA No.1995-234322, with tensile stress be arranged on 10 the gram or more than, preferably it is arranged on 100 the gram or below so that as disclosed among the JPA No.1995-234324 can residual stress after wire drawing.In addition, also can adopt the method that before stretching, has the step of preheating.

Plastic optical fiber after third step is handled can be directly used in various application under the situation of not carrying out any modification.In addition, described fiber can also be having tectum or fibrolaminar form is carried out various application on its outer surface, and/or in order to protect or the enhanced purpose is used with the form of fibrous bundle.

For the situation that coating is provided to element line, covering method is as follows: make the die head of element line by a pair of opposition, die head has the through hole that the element fiber is passed through; Between the opposition die head, be filled with the molten polymer that coating is used, shift out the element fiber between the die head then.Consider to prevent the inner member fiber because crooked and stressed, preferably, tectum not with the element fiber fusion together.In this covering method, the element fiber is subjected to pyrolytic damage owing to contacting with molten polymer usually.Therefore, the translational speed of setting element fiber preferably so that make the thermal damage minimum, and is chosen in that fusible polymkeric substance is used to form tectum in the low temperature range.Tectal thickness can be according to the melt temperature that forms tectal polymkeric substance, the draw speed of element fiber, and tectal cooling temperature is regulated.

Be used for comprising forming tectal other currently known methods on the fiber: make the monomer that is applied on the optical component carry out the polymeric method, twine the method for sheet material, and make optical component pass through the method for the hollow tube that extrusion molding obtains.

The covering of element fiber enables to be used to prepare plastic optical fiber cable.The form that covers comprises: plastic optical fiber is capped interface that material covers both and tightens in whole circumference length and connect airtight the contact of touching and cover; With gapped at the interface loose covering at covering material and plastic optical fiber.Since when a tectal part usually when peeling off with the joining region of junctor, loose covering tends to make water to enter the gap from tectal end, and along its longitudinal diffusion, therefore, preferred usually contact covering.Yet, because tectum can alleviate most infringements, as put on stress or heat on the cable, and therefore can reduce infringement the element fiber, therefore, tectum also is preferably applied in some application with the loose covering that the element fiber does not closely contact.By filling the gap, can avoid diffusion from the water of end face with liquid gel, semi-solid state or powder material.If semi-solid state or powder material also have other function except anti-sealing diffusion function, as improve thermotolerance, mechanical property etc. have more high performance covering with acquisition.

Form clearance layer by joint location and the control reliever of regulating straight type matrix head, can obtain loose covering.The thickness of clearance layer can be by the thickness of control joint, or clearance layer pressurizeed/reduce pressure regulate.

In addition, can also provide another tectum (second tectum), so that surround existing tectum (first tectum).Can add fire retardant in second tectum, the UV absorption agent, oxidation inhibitor, the radical trapping agent, lubricant or the like, these additives also can be included in first tectum, as long as can guarantee satisfied anti--moisture-perviousness.

Although the known resin that comprises bromine or other halogen or phosphorus or additive are arranged as fire retardant,, consider security as reducing the discharging of poison gas, the resin or the additive that comprise metal hydroxides become main flow just day by day.In its structure of metal hydroxides crystal water is arranged, this makes can not fully remove combination water in process of production, therefore, preferably its as the outer cover (second tectum) around anti--moisture-perviousness layer (first tectum) of the present invention so that fire-retardant covering to be provided.

Can also the tectum stack of multiple function will be had in addition.For example, except that fire-retardant, can also provide the blocking layer that prevents the moisture absorption of element fiber, or the moisture adsorbent layer that dewaters, be typically in tectum or between moisture-absorbing band or absorbent gelling.In addition, can also be provided for the crooked flexible material layer that discharges stress down, cushioning material such as foam layer, and be used to strengthen the inflexible enhancement Layer, all these all can be selected according to various objectives.Except that resin, as structured material, preferably highly elastic fiber (being called the tensile strength fiber) and/or wire rod such as height-rigid metal line are added in the thermoplastic resin, this will strengthen the physical strength of the cable that obtains.

The example of tensile strength fiber comprises aramid fiber, trevira and tynex.The example of metal wire comprises stainless steel wire, zinc alloy wire and copper cash.Wherein both all only are not confined to above-mentioned example.Any other protective layer as metal tube, is used for the subordinate line of built on stilts cable, and the device that is used to improve workability during connecting up includes interior.

The type of cable comprises: the set cable with concentric bundle element fiber; Belt conductor with linear gauging element fiber; And the set cable that makes it further bunchy by compacting winding or wrap jacket; All these all can suitably be selected according to concrete application.

Optical component of the present invention can be used for as optical cable in the system of transmitting optical signal, and described system comprises various luminous elements, light-receiving element, other optical fiber, optical bus, optical reflective star coupler, light signal processing device, optical connector that is used to connect or the like.Any known technology all can be used reference: " Purasuchikku Oputicaru Faiba no KisotoJissai (Basics and Practice of Plastic Optical Fiber) ", (N.T.S.Co., Ltd. publishes); As typically being described in JPA Nos.hei10-123350, the optical bus among 2002-90571 and the 2001-290055; Typically be described in JPA Nos.2001-74971,2000-329962,2001-74966,2001-74968, the optical frequency branch/coupling device among 2001-318263 and the 2001-311840; Typically be described in the optical reflective star coupler among the JPA No.2000-241655; Typically be described in JPA Nos.2002-62457, light signal transmission device among 2002-101044 and the 2001-305395 and optical data highway system; Typically be described in the optical signal processor among the JPA No.2002-23011; Typically be described in the optical signal intersection-connected system among the JPANo.2001-86537; Typically be described in the optical transmission system among the JPANo.2002-26815 and typically be described in multifunction system among JPA Nos.2001-339554 and the 2001-339555.

Outside above-mentioned application, optical component of the present invention can also be applied to various technical fields, as lighting system, and energy emitter, set lights or transmitter.

Embodiment

Below with reference to object lesson the present invention is specifically described.It is pointed out that do not breaking away under the spirit of the present invention, any material, reagent, usage ratio, operation or the like all can be carried out appropriate change.Therefore, in any case scope of the present invention also is not limited to as follows

Specific embodiment.

Embodiment 1-1

To comprise deuterate MMA (MMA-d8) as polymerisable monomer (wherein removed as the hydroquinone monomethyl ether of stopper and water-content is reduced to and be not more than 80ppm), with respect to the benzoyl peroxide as polymerization starter (BPO) of this monomer weight 0.5 weight %, with pouring internal diameter with respect to monomer weight 0.28 weight % into as an amount of mixture of the positive lauryl mercaptan of chain-transfer agent is that 22 millimeters, length are that its internal diameter is consistent with the external diameter of acquisition preformed articles in the enough inflexible cylindrical vessels of 600 millimeters have.This container is placed 80 ℃ water-bath and make mixture in 80 ℃ of vibration prepolymerizations 2 hours.Subsequently, when making container maintenance level and making its rotation, under heating, made polymerization of mixtures 3 hours in 80 ℃ with 3000rpm, then in 100 ℃ to its thermal treatment 24 hours, thereby obtain hollow circular cylinder by the polymer of MMA-d8.

Then, will be as the MMA-d8 of polymerisable monomer (wherein removed as the hydroquinone monomethyl ether of stopper and water content is reduced to and be not more than 80ppm), with respect to above-claimed cpd (13), (16) or 28 of this monomer weight 10 weight %, or mix as a comparison case compound (34), (35) or (36) as described below.Described mixing solutions is directly poured in the hollow region of the hollow circular cylinder that obtains by the membrane filter based on tetrafluoroethylene in 0.2 micron in aperture.Will being added in this mixing solutions with respect to monomer weight 0.016 weight % as the PDB of polymerization starter with respect to the positive lauryl mercaptan of monomer weight 0.27 weight % as chain-transfer agent.In this system, the chain transfer constant of positive lauryl mercaptan is 0.8.The right cylinder that is introduced into mixing solutions is placed the Glass tubing of diameter than this right cylinder external diameter big 9%, and make it vertically to place the pressure polymerization reactor.Use the internal atmosphere of nitrogen purge pressure polymerization reactor then, be forced into 0.6MPa, and 100 ℃ of thermopolymerizations of carrying out 48 hours, subsequently when keeping pressurization atmosphere in 120 ℃ of polymerizations 24 hours, obtain preformed articles thus.

When polymerization is finished, the preformed articles that obtains is observed discovery, do not comprise any bubble that may introduce by volumetric shrinkage.Preformed articles is carried out thermal stretch at 230 ℃, so that form the plastic optical fiber of the about 700-800 micron of diameter.Do not find that during stretching preformed articles has bubble, this will successfully obtain 300 meters long fibers with stable manner.

Each the optical fiber that obtains list among the table 1-1 in the transmission loss of 850nm light source and transmission band, wherein provided the Hammett value that is used for various fibre-optic doping agents and belonged to the residing wavelength value of absorption peak of the 4th overtone of phenyl ring C-H stretching vibration.

It is to be noted, the Hammett value of compound (35) is the value when all C-D keys all are considered to c h bond, and can ignore substantially in 99.5% o'clock owing to the absorption peak that belongs to the 4th overtone of C-H stretching vibration is not less than in the deuterate rate, so this absorbing wavelength of compound (35) is not listed among the table 1-1.

, because the Tg due to these doping agents descends every kind of doping agent of 10 weight % is added among the MMA-d8 for research, makes MMA-d8 carry out mass polymerization, measure the Tg of each mass polymer that is obtained then.The Tg value that is obtained is listed among the table 1-2.

Embodiment 1-2

With aforesaid MMA-d8 (wherein removed as the hydroquinone monomethyl ether of stopper and water content reduced to and be not more than 80ppm), be used as polymerisable monomer with the mixture of fluoridizing deuterate monomer 3FM-d7 as follows, wherein, the weight ratio of the former with the latter is 9: 1.With 8 weight % with embodiment 1-1 in employed identical doping agent, promptly compound (13), (16), (28), (35) or (36) are added in this monomer mixture.Except that these, use the mode identical to produce optical fiber with embodiment 1-1.

The optical fiber of each acquisition is listed in table 1-3 in the transmission loss and the transmission band of 850nm light source and the Hammett value that is used for each fibre-optic doping agent.

Embodiment 1-3

With aforesaid MMA-d8 (wherein removed as the hydroquinone monomethyl ether of stopper and water content reduced to and be not more than 80ppm), with the mixture of deuterate monomer tBMA-d14 as follows as polymerisable monomer, wherein, the weight ratio of the former with the latter is 1: 1.With 10 weight % with embodiment 1-1 in employed identical doping agent, promptly compound (13), (16), (28), (35) or (36) are added in this monomer mixture.Except that these, use the mode identical to produce optical fiber with embodiment 1-1.

The optical fiber of each acquisition is listed in table 1-4 in the transmission loss and the transmission band of 850nm light source and the Hammett value that is used for each fibre-optic doping agent.

Table 1-1

Monomer	Doping agent	The Hammett value	Transmission loss [dB/km]	Transmission band [GHz/km]	Wavelength ^*[nm]
Monomer	Doping agent	The Hammett value	Transmission loss [dB/km]	Transmission band [GHz/km]	Wavelength ^*[nm]	?MMA-d8	????(13)	????-0.073	??99	????1.0	??880
?MMA-d8	????(16)	????-0.28	??97	????1.0	??883	?MMA-d8	????(13)	????-0.073	??99	????1.0	??880
?MMA-d8	????(16)	????-0.28	??97	????1.0	??883	?MMA-d8	????(28)	????-0.17	??102	????1.0	??882
?MMA-d8	????(34)	????0.134	??400	????1.0	??873	?MMA-d8	????(28)	????-0.17	??102	????1.0	??882
?MMA-d8	????(34)	????0.134	??400	????1.0	??873	?MMA-d8	????(35)	????(0.294)	??100	????0.7	??-
?MMA-d8	????(36)	????0.578	??720	????0.7	??867	?MMA-d8	????(35)	????(0.294)	??100	????0.7	??-

^*: the absorption peak wavelength that belongs to the 4th overtone of phenyl ring C-H stretching vibration

Table 1-2

Monomer	Doping agent	????Tg ^**[℃]
Monomer	Doping agent	????Tg ^**[℃]	????MMA-d8	????(13)	????89
????MMA-d8	????(16)	????90	????MMA-d8	????(13)	????89
????MMA-d8	????(16)	????90	????MMA-d8	????(28)	????90
????MMA-d8	????(34)	????82	????MMA-d8	????(28)	????90
????MMA-d8	????(34)	????82	????MMA-d8	????(35)	????81
????MMA-d8	????(36)	????87	????MMA-d8	????(35)	????81

^*: the Tg that contains the polymkeric substance of 10 weight % doping agents

Table 1-3

Monomer	Doping agent	The Hammett value	Transmission loss [dB/km]
Monomer	Doping agent	The Hammett value	Transmission loss [dB/km]	?MMA-d8/3FM-d7(9∶1)	????(13)	????-0.073	????98
?MMA-d8/3?FM-d7(9∶1)	????(16)	????-0.28	????102	?MMA-d8/3FM-d7(9∶1)	????(13)	????-0.073	????98
?MMA-d8/3?FM-d7(9∶1)	????(16)	????-0.28	????102	?MMA-d8/3?FM-d7(9∶1)	????(28)	????-0.17	????100
?MMA-d8/3?FM-d7(9∶1)	????(34)	????0.134	????405	?MMA-d8/3?FM-d7(9∶1)	????(28)	????-0.17	????100
?MMA-d8/3?FM-d7(9∶1)	????(34)	????0.134	????405	?MMA-d8/3?FM-d7(9∶1)	????(35)	????-	????101
?MMA-d8/3?FM-d7(9∶1)	????(36)	????0.578	????751	?MMA-d8/3?FM-d7(9∶1)	????(35)	????-	????101

Table 1-4

Monomer	Doping agent	The Hammett value	Transmission loss [dB/km]
Monomer	Doping agent	The Hammett value	Transmission loss [dB/km]	?MMA-d8/tBMA-d14(1∶1)	????(13)	????-0.073	??101
?MMA-d8/tBMA-d14(1∶1)	????(16)	????-0.28	??99	?MMA-d8/tBMA-d14(1∶1)	????(13)	????-0.073	??101
?MMA-d8/tBMA-d14(1∶1)	????(16)	????-0.28	??99	?MMA-d8/tBMA-d14(1∶1)	????(28)	????-0.17	??99
?MMA-d8/tBMA-d14(1∶1)	????(34)	????0.134	??402	?MMA-d8/tBMA-d14(1∶1)	????(28)	????-0.17	??99
?MMA-d8/tBMA-d14(1∶1)	????(34)	????0.134	??402	?MMA-d8/tBMA-d14(1∶1)	????(35)	????-	??98
?MMA-d8/tBMA-d14(1∶1)	????(36)	????0.578	??710	?MMA-d8/tBMA-d14(1∶1)	????(35)	????-	??98

To shown in the table 4, have found that as table 1 when using Hammett value greater than particular value, promptly when 0.04 compound (34) or (36), the transmission loss when use compound (35) is compared in the transmission loss at 850nm place is much bigger; And when using Hammett value to be not more than 0.04 compound (13), (16) or (28), the fibre-optic transmission loss that the fibre-optic transmission loss that is obtained is obtained during with use compound (35) is in identical level.

Have found that, when using doping agent of the present invention, compare during with use compound (35), under the identical situation of addition, will obtain wideer transmission band, and, therefore will obtain better resistance toheat because polymkeric substance has higher Tg.

Embodiment 2-1 and 2-2 and Comparative Examples 2-1

With the weight ratio of deuterated methyl methacrylate MMA-d8 and IBOMA IBXMA (both have all removed as the hydroquinone monomethyl ether of stopper and water-content is reduced to and have been not more than 80ppm) the former with the latter is that to pour internal diameter into be that 22 millimeters, length are that its internal diameter is consistent with the external diameter of acquisition preformed articles in the enough inflexible cylindrical vessels of 600 millimeters have for 4: 1 an amount of monomer mixture.To be added in this monomer mixture with respect to the benzoyl peroxide as polymerization starter (PDB) of monomer mixture weight 0.5 weight % with respect to the positive lauryl mercaptan of monomer mixture weight 0.28 weight % as chain-transfer agent.Container is placed 80 ℃ water-bath and make mixture in 80 ℃ of vibration prepolymerizations 2 hours.Subsequently, when making container maintenance level and making its rotation, under heating, made polymerization of mixtures 3 hours in 80 ℃ with 3000rpm, then in 100 ℃ to its thermal treatment 24 hours, thereby obtain the hollow circular cylinder that the multipolymer by MMA-d8 and IBXMA makes.

Then, it with the weight ratio of MMA-d8 and IBXMA (both have all removed as the hydroquinone monomethyl ether of stopper and water content is reduced to and have been not more than 80ppm) the former with the latter 4: 1 monomer mixture, with above-claimed cpd 2-(4) or 2-(6) with respect to this monomer mixture weight 12.5 weight %, or control compounds 2-as described below (19) mixing, obtain mixing solutions thus.Described mixing solutions is directly poured in the hollow region of the hollow circular cylinder that obtains by the membrane filter based on tetrafluoroethylene in 0.2 micron in aperture.Will being added in this mixing solutions with respect to monomer mixture weight 0.016 weight % as the PBD of polymerization starter with respect to the positive lauryl mercaptan of monomer mixture weight 0.27 weight % as chain-transfer agent.In this system, the chain transfer constant of positive lauryl mercaptan is 0.8.The right cylinder that is introduced into mixing solutions is placed the Glass tubing of diameter than this right cylinder external diameter big 9%, and make it vertically to place the pressure polymerization reactor.Use the internal atmosphere of nitrogen purge pressure polymerization reactor then, be forced into 0.2MPa, and 100 ℃ of thermopolymerizations of carrying out 48 hours, subsequently when keeping pressurization atmosphere in 120 ℃ of polymerizations 24 hours, obtain preformed articles thus.

Control compounds 2-(19)

σ＝-0.114

SP value 11.0

Measure each the optical fiber that obtains for the transmission loss of 850nm light source.And being in temperature is that 25 ℃ and RH are under 95% the condition, measure once more each the optical fiber that obtains for the transmission loss of 850nm light source.The increment of transmission loss is listed among the table 2-1.

Embodiment 2-3 and 2-4 and Comparative Examples 2-2

By (" KF-#850 " is by Kureha ChemicalIndustry, Co. to poly (vinylidene fluoride) (PVDF), Ltd. make) carry out extrusion molding, produce 20 millimeters of external diameters, 19 millimeters of internal diameters, the PVDF pipe that 0.5 millimeter of thickness and length are 600 millimeters is as clad region. will comprise deuterate methyl methacrylate MMA-d8 and wherein the methacrylic acid ester moiety be 7: 3 monomer mixture by the weight ratio of the IBOMA IBXMA-d5 of deuterate (wherein both have all removed as the quinhydrones monomethyl ether of polymerization inhibitor and water content is down to and have been not more than 80ppm) the former with the latter; With the BPO as the polymerization initator with respect to this monomer mixture weight 0.5 % by weight, and pour in the middle dummy section of the PVDF pipe that obtains by the molecular filter based on tetrafluoroethene in 0.2 micron in aperture with respect to the polymerisable compound as the positive lauryl mercaptan of chain-transferring agent of monomer mixture weight 0.28 % by weight. 80 ℃ of of vibration of The PVDF pipe that is introduced into polymerisable compound is placed 80 ℃ of water-bath and make polymerisable compound in prepolymerizations, 2 hours.Subsequently, make and guarantee that water holding is flat and with the 3000rpm rotation, 100 ℃ of it is of 80 ℃ of .At of make polymerisable compound polyase 13 hour at carried out, 24 hours thermal treatment then.So, formed the outer core district that makes by multipolymer.

Then, it with the weight ratio of MMA-d8 and IBXMA-d5 (both have all removed as the hydroquinone monomethyl ether of stopper and water content is reduced to and have been not more than 80ppm) the former with the latter 7: 3 monomer mixture, with above-claimed cpd 2-(4) or 2-(6) as doping agent with respect to this monomer mixture weight 12.5 weight %, or aforesaid control compounds 2-(19) mixing, obtain mixing solutions thus.Described mixing solutions is directly poured in the hollow region of the hollow circular cylinder that obtains by the membrane filter based on tetrafluoroethylene in 0.2 micron in aperture.Will being added in this mixing solutions with respect to monomer mixture weight 0.016 weight % as the PBD of polymerization starter with respect to the positive lauryl mercaptan of monomer mixture weight 0.27 weight % as chain-transfer agent.In this system, the chain transfer constant of positive lauryl mercaptan is 0.8.The right cylinder that is introduced into mixing solutions is placed the Glass tubing of diameter than this right cylinder external diameter big 9%, and make it vertically to place the pressure polymerization reactor.Use the internal atmosphere of nitrogen purge pressure polymerization reactor then, be forced into 0.2MPa, and 100 ℃ of thermopolymerizations of carrying out 48 hours, subsequently when keeping pressurization atmosphere in 120 ℃ of polymerizations 24 hours, obtain preformed articles thus.

When polymerization is finished, the preformed articles that obtains is observed discovery, do not comprise any bubble that may introduce by volumetric shrinkage.Preformed articles is carried out thermal stretch at 230 ℃, so that form the about 500 microns plastic optical fiber of diameter.Do not find that during stretching preformed articles has bubble, this will successfully obtain 300 meters long fibers with stable manner.

Measure each the optical fiber that obtains for the transmission loss of 850nm light source.And being in temperature is that 25 ℃ and RH are under 95% the condition, measure once more each the optical fiber that obtains for the transmission loss of 850nm light source.The increment of transmission loss is listed among the table 2-2.

Then, with polyethylene each the fibre-optic outside surface that is obtained in embodiment and the Comparative Examples is coated with, form first coating of 0.75 millimeter of thickness thus, carry out the secondary coating with the polyethylene that comprises 3% carbon again, form second coating of 0.75 millimeter of thickness thus.Respectively it is carried out pliability test.Described pliability test is carried out according to the method that is described among the JPA No.1995-244220.Specifically, make crooked 90 degree of coated fiber once, measure then because the optical transmission loss due to the bending by the axle of twining 60 mm dias.Because the maximum value of the transmission loss due to the bending is listed among the table 2-2.

Table 2-1

	Doping agent	Transmission loss [dB/km]	The increment of transmission loss [dB/km]	Transmission loss due to the bending [dB]
	Doping agent	Transmission loss [dB/km]	The increment of transmission loss [dB/km]	Transmission loss due to the bending [dB]	Embodiment 2-1	??(4)	??510	??290	??0.7
Embodiment 2-2	??(6)	??495	??280	??0.7	Embodiment 2-1	??(4)	??510	??290	??0.7
Embodiment 2-2	??(6)	??495	??280	??0.7	Comparative Examples 2-1	??(19)	??770	??350	??1.0

Table 2-2

	Doping agent	Transmission loss [dB/km]	The increment of transmission loss [dB/km]	Transmission loss due to the bending [dB]
	Doping agent	Transmission loss [dB/km]	The increment of transmission loss [dB/km]	Transmission loss due to the bending [dB]	Embodiment 2-3	??(4)	??420	??220	??0.05
Embodiment 2-4	??(6)	??405	??210	??0.05	Embodiment 2-3	??(4)	??420	??220	??0.05
Embodiment 2-4	??(6)	??405	??210	??0.05	Comparative Examples 2-2	??(19)	??680	??270	??0.07

As show to have found that shown in 2-1 and the 2-2, when the doping agent that uses SP value greater than 10.9, promptly during control compounds (19), initial transmission loss and to shelve the increment of transmission loss afterwards under wet heat condition all very big; And when using SP value to be not more than 10.9 compound 2-(4) or 2-(6), will the good result of acquisition.Also find in addition, when fiber is coated with, with obtaining good result, as very low by the caused transmission loss of bending.

Industrial applicibility

On the one hand, the invention provides a kind of polymerisable compound that can produce at low cost for the optical component of 850nm wavelength, and the optical component that has the low transmission loss at the 850nm wavelength.

On the other hand, the invention provides and a kind ofly can produce the polymerisable compound that has the optical component of low transmission loss and well water-fast-heat resistance at the 850nm wavelength, and the optical component that has the low transmission loss and have well water-fast-heat resistance at 850nm.

Claims

1. a production is used for the polymerisable compound of the optical component of 850nm wavelength, comprises:

Polymerizable monomer component,

Polymerization starter and

Specific refractory power is different from the compound of described polymerizable monomer component, and its structure has the phenyl ring of a plurality of substituting groups replacements that are not more than by the Hammett value that substituting group of 0.04 replaces or are not more than 0.04 by Hammett value mean value.

2. the polymerisable compound of claim 1, wherein, described polymerizable monomer component comprises at least a monomer that is selected from the ester of acrylic acid ester and its derivative that accounts for major portion.

3. the polymerisable compound of claim 2, wherein, described polymerizable monomer component comprises the monomer of the ester of the acrylic acid ester of at least a being selected from (methyl) that accounts for major portion and its derivative.

4. the polymerisable compound of claim 1, wherein, described polymerizable monomer component comprises at least a material that is selected from the compound with C-F key.

5. the polymerisable compound of claim 1, wherein, described polymerizable monomer component comprises at least a material that is selected from the compound of (deuterium) key that has C-D.

6. optical component of being produced by the polymerization of the composition of claim 1 is so that form the zone with gradation refractive index.

7. optical component that is used for the 850nm wavelength, it comprises:

Have the compound of different refractivity with described polymer composition, wherein, described compound be not shorter than the 875nm place have owing to phenyl ring in the absorption peak of the 4th overtone of c h bond stretching vibration.

8. the optical component of claim 7, wherein, described compound is selected from the compound of structural formula (1):

Structural formula (1)

In structural formula (1), R ¹-R ¹⁰Represent hydrogen atom separately, alkyl, thiazolinyl, alkoxyl group, alkene oxygen base or dialkylamino, precondition is wherein to represent alkyl, thiazolinyl, alkoxyl group, alkene oxygen base or dialkylamino at least four.

9. the optical component of claim 7, it comprises the zone with gradation refractive index.

10. the optical component of claim 9, it comprises along the center zone that outwardly direction has gradation refractive index.

11. a polymerisable compound that is used to produce optical component comprises:

Comprise at least a polymerizable monomer component that is selected from the compound of following structural formula (2): structural formula (2)

Wherein, X ¹Be hydrogen (H) or deuterium (D), wherein two X ¹Can be identical or different; Y ¹Expression H, D, CH ₃Or CD ₃And R ¹Expression C _7-20Alicyclic hydrocarbon radical;

Polymerization starter and

Specific refractory power is different from described polymerizable monomer component and solubility parameter is not more than 10.9 compound, and its structure has the phenyl ring of a plurality of substituting groups replacements that are not more than by the Hammett value that substituting group of 0.04 replaces or are not more than 0.04 by Hammett value mean value.

12. the polymerisable compound of claim 11, wherein, polymerizable monomer component comprises methacrylic acid alicyclic hydrocarbon methyl ester and the methyl methacrylate that accounts for major portion.

13. the polymerisable compound of claim 12, wherein, polymerizable monomer component comprises the compound of at least a C-D of containing key.

14. an optical component of being produced by the polymerization of the composition of claim 11 is so that form the zone with gradation refractive index.

15. the optical component of claim 14 comprises the core district with gradation refractive index and the clad region in the described core of covering district, described core district is made by the polymerization of the composition of claim 11.

16. the optical component of claim 15, wherein, the core district has along the center zone that outwardly direction has gradation refractive index.

17. the optical component of claim 15, wherein, clad region is mainly formed by polymerizable monomer component, and described monomer component has the composition identical with the core district or most of identical composition.

18. the optical component of claim 15, it is optical fiber, photoconduction or optical lens.

19. the production method of an optical component comprises the polymerisable compound step of polymerization that makes claim 1.

20. the method for claim 19, wherein, in described polymerization procedure, polymerization temperature is 50 ℃ or higher.